Metalliferous azo-dyestuffs



METALLIFEROUS AZO-DYESTUFFS Alfred Fasciati, Bottmingen, Switzerland,assignor to Ciba Limited, Basel, Switzerland, aSwiss firm No Drawing. Application October 17, 1955 Serial No, 541,041

Claims priority, application Switzerland December 21, 1951 11 Claims. (Cl. 260-447 in which Y represents an amino hydroir'yl group, R

represents a benzene radical bound to'the'az'o linkage ,in ortho-position to the hydroxyl represents the radical of a coupling component bound to the azo linkage in a position vicinal to the. group Y, n represents a whole number not greaterthan 7, m represents the whole number 1 or 2, and X represents an aryl radical containing the aforesaid single jcarboxylic acid group. I p t The monoaZo-dyestufls of the above formula serving as starting materials in the present process can be made by coupling a coupling component free from sulfonic acid groups and carboxylicacid groups and capable of coupling in a position vicinal to an amino or hydroxyl group, with a diazotized amine free from sulfonic acid groups and corresponding to the general formula (2) O (|)IE[ O=iiR -NH,

which contains in the radical X a carboxylic acid group which is not present in a position vicinal to a hydroxyl or NH group (i.e. the said carboxylic acid group is the only salt forming group present in the radical X), the symbols R n, m and X having the meanings given in connection with Formula 1.

The benzene radical R of these amines, which contains the amino group in the 2-position and the hydroxyl group in the 1-position, may be bound to the SO group in the 4-, 5- or 6-position. It may contain further substituents incapable of salt formation, for example, an alkyl, alkoxy or acylamino group, a halogen atom or a nitro group. The aryl radical X may, for example, be

States Patent a naphthalene or advantageously a benzene radical which acetylamino-l-hydroxybenzene benzoyl-acetic acid phenylamide.

ice

in addition to the carboxylic acid group may contain further substituents which do not impart solubility in water, such as an alkyl group (for example, methyl), a methoxy group, a chlorine atom or the like.

' As amines of the Formula 2 there may be mentioned: Z-amino-1-hydroXybenzene-4-sulfonic acid-N-2-naphthylamide-3 carboxylic acid, 2-amino-1-hydroxy-6-chlorobenzene-4-sulfonic acid phenylamide-2-carboxylic acid, 2-amino-1-hydroxy-6-nitrobenzene-4-sulfonic acid phenylamide-2-carboxylic acid, 2-amino-1-hydroxybenzene-4- or 5-sulfonic acid N-methylpheny1amide-2 carboxylic acid, 2-amino-1-hydroxybenzene-4 or 5-su1fom'c acid phenylamide-2'-, 3'- or -4-carboxylic acid, 2-an1ino-4-chloro-l-hydroxybenzene-S- or -6-sulfonic acid phenylamide- 2-carboxylic acid, 3-amino-4-hydroxydiphenylsulfone-2'- carboxylic acid and 4-amino-3-hydroxydiphenylsulfone- 2'- or -4-carboxylic acid;

As coupling components for preparing the monoazo- .dyestufls serving as starting materials in the present process there come into consideration amino-compounds or advantageously hydroXy-compounds, which are capable of coupling in a position vicinal to the amino or hydroxyl group. As amino-compounds of this kind there may be mentioned, for example, naphthylamines such as finaphthylamine, 2-naphthylamine-6-sulfonic acid amide and the like. By hydroxy-compounds there are to be understood aromatic hydroxy-compounds as well as compounds which owe their capacity for coupling to the presence of a keto-methylene group, since it is generally recognized that after coupling these latter compounds are present in the enol form, that is to say, they contain a hydroxyl group'in a position vicinal to the azo linkage. The latter compounds may contain the keto-methylene group either in an open chain or in a heterocyclic ring.

As hydroXy-compounds of the aforesaid kind there 'may be mentioned: Para-substituted hydroxybenzenes such as 4-methy1-, 3:4-dimethyl-, 4-tertiary-amylor 4- and 4-methyl-2-acetylamino-l-hydroxybenzene. Dihydroxybenzenes such as resorcinol, hydroxynaphthalenes such as 2-hydroxynaphthalene, 2:6-dihydroxynaphthalene, 2-hydroxy-6-bromoor -6-methoxynaphthalene, 2-hydroxynaphthalene-6-sulfonic acid anilide, 2-hydroXynaphthalene-6- or -7-sulfonic acid phenyl ester and 1-hydroxy-4-metl1ylnaphthalene, 1- hydroxy-S-chloronaphthalene, 1-hydroxy-5:8 dichloronaphthalene, and also 1-hydroxynaphthalene-3-, -4- or -5- sulfonic acid isopropylamide, 1-acy-lamino-7-hydroxynaphthalene such as 1-acety1amino-,'l-n-butyrylaminoor 1-benzoylamino-7-hydroxynaphthalene, 7- hydroxynaphtyl-(1)-carbamic acid methyl, ethyl or phenyl ester. Pyrazolones such as 3-methy1- or 3-phenyl-5-pyrazolone, 1-n-butyl-3-methyl-5 pyrazolone, 1 phenyl 3- methyl-S-pyrazolone, 1-(2'-, 3- or 4'-chloro)-phenyl-3- methyl-S-pyrazolone, 5-pyrazolone 3 carboxylic acid amides such as 5-pyrazolone-3-carboxylic acid amide, 5- pyrazolone-3-carboxylic acid-N-methyl-, ethyl-, isopropylor -butylamide, 5-pyrazolone-3-carboxylic acid- 2'- 3'- or 4'-chlorophenylamide, 5-pyrazolone-3-carboxylic acid-phenylor paramethylphenylamide, lphenyl-5-pyrazolone-3-carboxylic acid amide, l-phenyl-S- pyrazolone-3-carboxylic acid methyl-, -isopropyl-, phenylor para-chlorophenylamide, barbituric acids such as barbituric acid itself, dihydroxyquinolines such as 2:4-dihydroxyquinoline, acylacetic acid esters or amides such as acetoacetic acid ethyl or phenyl ester, acetoacetic acid amide, acetoacetic acid-methyl-, -butylor -phenyl-amide, acetoacetic acid-dimethy-lamide, acetoacetic acid-2'-, -3',- or -4'-chlorophenylarnide, benzoyl-acetic acid amide, and Especially valuable results are obtained with those of the compounds listed whose molecular weight is relatively The amines of the Formula 2 may he diazotized in the usual manner, for example, with the use of sodium nitrite and hydrochloric acid. Coupling of the resulting diazo compounds with the aforesaid coupling components can also be carried out in the usual manner, for example, in an acid to neutral medium, when the coupling component is capable of coupling in a position 'vicinal to an amino group, and advantageously in an alkaline medium when hydroxy'compounds are used as coupling components. a r When the coupling reaction is finished the dyestuffs can be separated from the coupling mixture easily by filtration, since they are in general only slightly soluble in'water. I

With agents yielding cobalt, compounds of the l :2-type are easily obtained and are especially-valuable.

The treatment with an agent yielding cobalt is advantageously carried out in such manner that the resulting cobaltiferous azo-dyestufi contains one atom of cobalt in complex union with two .monoazo-dyestufl molecules. 1 For this purpose it is generally desirable to use a quantity of the agent yielding metal corresponding to one gram-atom of metal for every two molecular proportions of a dyestulf of the general Formula -1 or for about one molecular proportion of each of two different monoazo-dyestufifs free from sulfonic acid groups in a mixture of such dyestufi's of which at least one corresponds to the general Formula 1, and/or to carry out the metallization in a weaklyacid toalkaline medium. Accordingly, there are suitable, for example, those metal compounds which are stable to alkaline media, for example, cobalt compounds of aliphatic ortho hydroxycarboxylic acids, which compounds contain the metal in complex union. As examples of aliphatic hydroxycarboxylic acids there may be mentioned inter *alia lactic acid, glycollic acid, citfic acid and especially taracid. As agents yielding cobalt there also come into consideration simple salts of divalent cobalt such as -cbalt sulfate, cobalt acetate, or cobalt "formate, if desired also cobalt hydroxide. Conversion of the dyestuffs into their complex metal compounds is advantageously carried out at a raised temperature, *under atmospheric or superatmospheric pressure, ,for example, :at the boiling temperature of the reaction mixture, if de- "sired in the presence of suitable additions for example, in the presence of salts of organic acids, bases, organic solvents or other agents assisting the formation ofcomplexes. V

The metallization treatment described above may be applied, 'for example, to a singledyestufl of the formula "1. 1 However, it is also possible and is in "many cases of advantage (for example, in order 'to produce difier- 'ent tints) to metallize a mixture of two different dyestuffs of that formula or a mixture consisting of a dyestuff of the said formula and another metallizable monoazo-dyestulf free from sulfonic acid and advantageously also free from carboxylic acid ggroups,v for example, an -ort-ho:ortho'-di-hydroxy -=monoazo-dyestuif.

'Themonoazo-dyestuifs to-be usedasstatting materials in the last mentioned "form of the process "together with -dyestuflFs-of the Formula 1, may be of any desired constitution provided-that they are free from sulfonicacid groups and advantageously also 'free 'from carboxylic acid groups. There come intoconsideration'both ortho: -ortho'-dihydroxyand ortho-hydroxy-orthocarboxy 'monoazo-dyestufl s which belong, for example, to the benzene-azo-benzene, benzene-azo-naphthalene, benzeneazo-pyrazolone or benzene-azo-acylacetic acid amide series. Thesemonoazo dyestuils can be madefrom .the

coupling components mentionedaboveby coupling them with diazo compounds of the lfol1owing. -amines: 4'chloro-, 4-nitro-, 4-methyl-2 amino l-ihydroxybenzene, 4;6- dichloroor 4:6sdinitror =amino-..1-hydroxybenzene, 4mi- 6-nitroor 6-ch1oro-4-acetylamino-2-am l-hy r xy enzene, 4-chloro-5- or -6-nitro2-amino-l-hydroxybenzene, 6-nitro-4-methyl-2-amino-l-hydroxybenzene, Z-amino-lhydroxybenzene-4- or -5-sul.fonic acid amide, and the corresponding N-methyl-, ethyb, -isopropyl-, octyl-, cyclohexyl-, -phenyl-, para-chlorophenyl-amides, and also 2- amino-L-hydroxybenzeneAF or 5 -sulonic acid dimethylamide or wN-.Inethylpltlcnylamide, Z-amho-l-hYdroxybenzene-4- or .-5-methylsu1tone, 3-.amino-4-hydroxy-diphenylsulfone, 4-amino-3-hydroxydiphenylsulfone, and also 5- nitro-Z-amino-I-hydroXybenZene, 2-aminobenzene-1-carboxylic acid, z-aminobenzene-l-car-boxylic acid-S-sulfonic acid amide, Z-aminohenzene-Lcarboxyliz: acid-,S-sulfonic acid methylor -phen yl amide, 2 -aminobenzene-l-carboxylie acid-S-methyl-suglfone and Z-aminobenzene-l-carboxylic acid-S-sulfonic acid phenyl ester.

The cobalt compounds so obtained contain two monoazo-dyestutf molecules bound to one atom of cobalt in complex union, and .at least mu: .of the monoazodyestutf molecules must correspond to the general For mnla 1. The new cobalt compounds are soluble in water, and are indeed more soluble than the starting materials used for making They are suitable for ldyteing .various substances such .as plastic masses, waxes, resins, lacquers and the like and especially 'for dyeing or printing synthetic substances composed of superpolyamides or superpolyurethanes, and above all for dyeing or printing animal materials such as silk, leather and especially wool. They are suitable for dyeing from a weakly alkaline 01'. neutral bath, and above all from a weakly acid, for example, acetic acid bath.

The dyeings so produced are distinguished by their good level character, good properties of wet fastness and very good .fastness. to light. 7

The following examples illustrate the invention, the parts and percentages "being by weight unless otherwise stated and the relationship of parts by weight to parts by volume being the same as that of the kilogram to the liter:

n Example 1 30,8 farts of khydrosy-21aminobenzene-4Tsu1fonic acid ,plienylamideef-carbozrylic acid are dissolved .in 150 partso'f waterandlz parts of a .1-0 .N-solution of caustic soda The resultinglclearsolutionis.med with ,25 parts or 'a 4 N-solution of sodium nitrite, and introduced drop- .wise .at .0-2 Chinto. armixture .of 1.10 parts of water and 4.0 parts of l0v N:hydrocbloric acid. The resulting pale vyellow diazoisuspension is neutralize with odi m carbonate, and added to an Lice-cooled solution of -9 parts of -1- (4 :l:i.lo1'4: phenyl e3.-methy1:5-pyr.azolone in 1250 parts of water, 110 partsof a .10 Nrsolutionlof caustic sodarandls partssof sodium carbonate. When thesaupling is finished the dyestuff is completely precipitated by the addition of sodium chloride and filtered ofl.

One half of the dyestufi filter cake so obtained is heated in 500 parts of water with '5 parts of a 10 N-solution of caustic soda to 80 tC., then mixed with a cobalt sulfate solution containing 1.52 parts of cobalt, and the whole is stirred. A further 4 parts of a 10 N-solution of caustic .sodaare .added,.and the mixtureis stirred iota-shor tim =-at.801 C. Zllhe-dyestufi :then pn cinitate by the addiztion of sodium-chloride and neutralization with acetic acid.

whenzdxyi is a brown-red:;pQWd.e h Q di olv in sodium carbonate solution With-axed brown coloration and in concentrated-sulfuric acid with ,a yellow brown coloration. ltdye 'wQol-troman utral or aceti -acid .bath fast yellow orangegtints.

2111;thQ-fOuQWjn gitableg vnithqprafierfiqs of fiurther complex .qmetal icolnpounds. obtainabl in an analogous lmanner. ..In -.colunm (a) Lisgiven-Jhetintofthenyeings .produced on swcol-rorsfihers ofia supi p lyamide with. th .cohalt' complex (oflthe dyestufi-l obtained irom the comtroor 4-ch1oro 6-acetylaniino-2-amino-l-hydroxybenzene, ponents given in columns I and II.

I II (a) Diam component Coupling component Cobalt complex 9 1. N H, 0113-0 O-CH5-NH Yellow.

0 O OH O N H O 2. -NH CHE-0 0-OHg-PJ-NH D0.

OaNH

C-----N 3.. NH, 1 Orange yellow. 0 0 0H CHx-C 0 E O NH 4. NH, OH Bordeaux.

0 O OH B1 OQNH OH NH-C o-om 5.. NH; HO- Violet grey.

C 0 OH O NH 6.. N H: OH Bordeaux.

OgNH

OH H0 01 7 N H, V olet.

11' Example 2 3.66 parts of the dyestufi obtained from diazotized nitro-2-amino-l-hydroxybenzene and 1-acetylaniino-7-hydroxynaphthalene and 5.27 parts of the dyestuff from diazotized Z-amino-l-hydroxybenzene-4-sulfonic acid anilide-2'-carboxylic acid and 1-(4'-chlorophenyl)-3-methy1- 5-pyrazolone are suspended in 200 parts of water, then mixed with 16 parts by volume of a 2 N-solution of sodium hydroxide, heated to 80 C., and mixed with 22 parts of a cobalt sulfate solution having a cobalt content of 2.95 percent. After heating the mixture for a short time at 78-82 C. the formation of the complex is finished. By the addition of sodium chloride and neutralization with dilute acetic acid, the cobalt compound is completely precipitated. After being filtered off and dried the dyestufi is a dark powder which dyes Wool from a weakly alkaline, neutral or weakly acid bath khaki tints.

In the following table are given further mixed cobalt complexes obtainable in an analogous manner from the monoazo-dyestuffs given in columns I and II. The dyestufls dye wool the tints given in column III.

12 groups and containing a single carboxylic acid group, which monoazo dyestufl corresponds to the formula number up to 7, m a whole number up to 2 and X a ben.

zene radical which contains as single salt forming group the said "carboxylic acid group.

2. A complex cdbalt compound containing one atom of I II III OH E0 on E0 C? fig 3......

somn-cn-cn, SOaNH I OOH no OH on no /CN 2..---- N=N--O I G1 N=N Brown.

t= on,

somn-cm-cm SOINH l E0 on HO OH o-NH 3..---. =N N=NG Brownish bordeaux.

C: (Bo-NH Br 01-6 (d ution. 802N119 coon Example 3 cobalt bound in complex union to substantially two mole- 2 parts of the cobaltiferous dyestulf obtained as described in Example 1 are dissolved in 4000 parts of water, 10 parts of crystalline sodium sulfate are added and 100 parts of well wetted wool are entered into the .resulting dyebath at 40-50 C. 2 parts of acetic acid of 40 percent strength are then added, the temperature is raised to the boil in the course of /2 hour, and dyeing is carried on at the boil for hour. Finally the wool is first rinsed with cold water and dried. The wool is dyed a fast yellow-orange tint of good fastness to light.

The same dyeing is obtained by dyeing from a neutral bath, that is to say without the addition of acetic acid to the bath.

What is claimed is:

1. A complex cobalt compound containing one atom of cobalt bound in complex union to .substantially two molecules of a monoazo dyestuif free from sulfonic acid cules of a monoazo dyestutf of the formula OOOH wherein Y represents a member of the group consisting of an amino and a hydroxyl group and R -Y represents the radical of a coupling component free from sulfonic and .carboxylic .acidgroups and bound .to the am linkage .ina position vicinal to the substituent Y.

3. A complex cobalt compound containing one atom of cobalt bound in complex union to substantially two molecules of a monoazo dyestuif of the formula COOH wherein R represents a benzene radical free from sulfonic and carboxylic acid groups.

A complex cobalt compound containing one atom of cobalt bound in complex union to substantially two molecules of a monoazo dyestufi of the formula COOH wherein Pz represents a 5-pyrazolone radical free from sulfonic and carboxylic acid groups and bound to the azo linkage in 4-position.

6. A complex cobalt compound containing one atom of cobalt bound in complex union to substantially two molecules of a monoazo dyestufi of the formula wherein R represents a Z-hydroxynaphthalene radical free from sulfonic and carboxylic acid groups and bound to the azo linkage in l-position.

7. A complex cobalt compound containing one atom of cobalt bound in complex union to substantially two molecules of a monoazo dyestufl of the formula OOOH wherein R represents a halogenated hydroxynaphthalene radical free from sulfonic and carboxylic acid groups and bound in a position vicinal to the azo linkage.

8. The complex cobalt compound containing one atom of cobalt bound in complex union with substantially two molecules of the monoazo dyestuif of the formula 1 Sci-NEG COOH 9. The complex cobalt compound containing one atom of cobalt bound in complex union with substantially two molecules of the monoazo dyestutf of the formula HO i a Q01 o Son-NH? 10. The complex cobalt compound containing one atom of cobalt bound in complex union with substantially two molecules of the monoazo dyestuft of the formula 11. The complex cobalt compound containing one atom of cobalt bound in complex union with substantially two molecules of the monoazo dyestuif of the formula SOs-NH COOH References Cited in the file of this patent UNITED STATES PATENTS 1,814,218 Holzach et a1 July 14, 1931 2,597,676 Schetty May 20, 1952 2,634,263 Steinemann Apr. 7, 1953 OTHER REFERENCES Row et al.: J. Soc. Dyers Colourists, vol. 62, 1946, 

1. A COMPLEX COBALT COMPOUND CONTAINING ONE ATOM OF COBALT BOUND IN COMPLEX UNION TO SUBSTANTIALLY TWO MOLECULES OF A MONOAZO DYESTUFF FREE FROM SULFONIC ACID GROUPS AND CONTAINING A SINGLE CARBOXYLIC ACID GROUP, WHICH MONOAZO DYESTUFF CORRESPONDS TO THE FORMULA 